Dinuclear clathrochelate complexes with pendent cyano groups as metalloligands

Area of Science:

• Coordination Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Dinuclear clathrochelate complexes are versatile building blocks in supramolecular chemistry.
• Functionalization of clathrochelates with cyano groups enables their use as metalloligands.
• The synthesis of complex coordination polymers (CPs) with tunable dimensionality and topology is an active area of research.

Purpose of the Study:

• To synthesize novel dinuclear clathrochelate complexes with varying numbers of peripheral cyano groups.
• To utilize these functionalized clathrochelates as metalloligands for constructing heterometallic coordination polymers.
• To investigate the structural diversity and topological properties of the resulting coordination polymers.

Main Methods:

• Synthesis of cyano-functionalized dinuclear clathrochelates via templated polycondensation or cross-coupling reactions.
• Coordination of clathrochelates with Zn(II)/Ag(I) or Co(II)/Ag(I) ions to form heterometallic coordination polymers.
• Characterization of the synthesized complexes and coordination polymers using single crystal X-ray diffraction and FT-IR spectroscopy.

Main Results:

• Successfully prepared dinuclear clathrochelate complexes with 2-5 peripheral cyano groups.
• Synthesized heterometallic coordination polymers (CPs) with varying dimensionalities (1D, 2D, and 3D) based on the clathrochelate's connectivity.
• Discovered a unique 3D coordination polymer exhibiting an unprecedented network topology with a high topological density and self-catenated structure.

Conclusions:

• Dinuclear clathrochelates with peripheral cyano groups are effective metalloligands for constructing diverse coordination polymers.
• The dimensionality and topology of the resulting CPs can be controlled by the functionalization degree of the clathrochelate ligand.
• The discovery of a novel, highly complex 3D network highlights the potential for designing intricate supramolecular architectures.